Process for converting gaseous hydrocarbons into liquid hydrocarbons



Dec. 13, 1938. E. c. MILLS 2,139,969 PROCESS FOR CONVERTING GASEOUS HYDROCARBONS INTO LIQUID HYDROCARBONS Filed Feb. 12, 1957 f/ugemy C. W

Patented Dec. 13,

PATENT OFFICE GASEOUS m- DROCABBONS INTO LIQUID HYDROCAR- BONS Eugene c. Mills, Berkeley, Calif. Application February 12, 931, Serial No. 125,447 6 Claim ,(Cl. 2021-31) My invention relates toQprocess'es for dehy-' drogenating flight hydrocarbons and thereby converting them into heavier hydrocarbons.

More specifically, it is applicable to the conversion of gaseous hydrocarbons, such as metha'ne,-into liquid hydrocarbons suitable for motor fuel and other uses.

This application is in part a continuation of my applicationflSerial No. 843 filed January 8,

An object of my invention is to provide a simple and inexpensive process for dehydrogen atinglight hydrocarbons and converting them into heavier-hydrocarbons.

light hydrocarbon to be dehydrogenated over a suitable catalyst in the presence of carbon at' high temperature, while maintaining a high frequency current ,in the catalyst and carbonaceous material, and condensing the resultant product. As the carbonaceous material and catalyst, I

prefer to employ' granulated coke impregnated I with cuprous chloride and I prefer to induce the high frequency current in the coke by positioning it in'a high frequency magnetic field.

The single figure of the drawing discloses an apparatus suitable for practicing my process.

There is shown in the drawing a still or retort l of tubular shape having an inlet pipe 2 at one' end and an outlet pipe 3 at the other end.

of-the worm of a condenser 5 and the outlet end of the worm terminates in a discharge spout 6. A casing I surrounds the worm 4 through which water is circulated by means of inlet and outlet pipes 8 and 9, respectively.

The retort l is made of heat resistant electrically nonconducting material, such as silica, or other vitreous material and is surrounded by a coil conductor l0, the terminals of which are connected to a source of high frequency altemating current II. In the drawing the source II is indicated as a mechanical generator but it is to be understood that any suitable source may be employed that is capable of providing the requisite amount of power at a suitable high frequency. The conductor l0 may consist of'copper tubing in accordance 'with the accepted practice in high frequency work.

The retort I is preferably completely fllled with the carbonaceous material to be employed.

'1his material is preferably ordinary coke, al-

though activated carbon, graphite or other forms of carbon may be used provided it is a conductor Essentially, my process comprises passing the.

The, outlet pipe connects with the inletend,

of electricity. The carbonaceous material is preferably formed in relatively small pieces to permit free passage of gas therethrough. Pieces A inch in diameter have been found suitable.

The coke or other material is preferably im- 5 -pregnated with a metallic salt constituting a catalyst. I prefer to provide cuprous chloride as the catalyst, although ferrous chloride and nickel chloride, among others, may be used.

Where coke and cuprous' chloride are em- 10 ployed, I prefer to soak the coke in a highly concentrated solution of cuprous chloride and then dry the coke in an oven at a temperature just high enough to drive oifi the water content.

In operation, when high frequency current is 15 supplied to the conductor [0 from the source II, a high frequency magnetic field is set up within the retort I, which field induces currents in the carbonaceous material within the retort, which currents heat the material to a suitable 20 temperature which may vary from approximately 350 C. to 1000 C., temperatures within the range 500 C. to 800 C. producing optimum results in my experimental work. After the coke has been fully heated, the gas to be treated, 25 such as natural gas or methane, is introduced through the pipe 2 and flows through the retort l and through the pipe.3 intothe worm 4 of the still I, wherecondensible liquid products are condensed and discharged from the spout 6. As 30 a result of the action of the heated coke and catalyst and the action of the high frequency magnetic field and the high frequency .currents induced thereby, a substantial portion of the gaseous hydrocarbon constituents entering the retort l are dehydrogenated to produce heavier hydrocarbons and hydrogen. The heavier hydrocarbons are condensed to liquid form in the worm L and discharged as liquid from the spout 8.. The hydrogen escapes from the spout 6 in 40 gaseous form.

In my experimental work I have obtained good results using energizing current of a frequency of about 10,000 cycles per second, but the frequency does not appear to be critical and the 46 exact frequency for greatest efliciency with any particular apparatus can be determined by test. My experiments indicate that the optimum frequency in commercial operation would prob- I ably be not less than 5000 cycles per second or I more than 20,000 cycles per second. The temperature of the carbonaceous material may be maintained at a suitable value by regulation of the current in the coil l0 since the necessary heat is produced by the flow of the 6 current induced in the carbonaceous material by the electromagnetic field developed by the current flowing in thecoll iii. Varying the current in the coil it) naturally varies the strength of the electromagnetic field which determines the magnitudes of the currents induced in the carbonaceous material. I prefer to'avoid arcs between the lumps or carbonaceous material and to this end the material is preferably tightly packed so that there is good electrical contact between the diflerent particles. The reactiorl desired appears to he brought about solely by the action of the high frequency electromagnetic field acting on the gas at the elevated temperature in the presence of the catalyst.

It is also essential that the catalyst employed on the suriaces of the carbonaceous particles shall be an electric conductor as otherwise the catalyst would prevent the formation of the secondary currents in the carbonaceous material. Arcsbetween the carbonaceous particles are objectionable because they would tend to break down, by their high temperature, the very compounm that it'is desired to obtain.

Although the invention has been explained by describing a particular specific procedure that may be employed and spectific apparatus that may he used, it is to he understood that other apparatus than that'disclosed may be used, and variations in the particular procedure described can. he made-Without departing from the invention, the scope of which is set forth in the appended claims.

I claim:

* 1. The process or converting gaseous hydrocarbons into liquid hydrocarbons which com prises subjecting the gaseous hydrocarbons to the action of a high frequency magnetic field" in the presence of solid carbonaceous material and a catalyst of theclass consisting of cuprous chloride, ferrous chloride and nickel chloride, at an elevated temperature, the high frequency magneticfield in conjunction with the catalyst at the elevated temperature causing thereaction to take place. I

2. The process of converting gaseous hydrocarbons into liquid hydrocar us which comprises passing the gaseous hydrocarbon through a mass oi granular carbonaceous terial imgoregnated with a catalyst of the class consisting of cuprous chloride, ferrous chloride and nickel chloride, positioned in a high frequency magarcaoce netic field of such intensity as to'heat said vcarhouaceous material to a temperature between 359 C. and room C. by current inducer} therein heat, and simultaneously inducing a high ireouency current in the solid absorbent material.

the high frequency induced current in conjunction with the catalyst at the elevated temperature causing the reaction to talre place.

4 The process of converting gaseous hydro carbons into liquid hydrocarbons which com= prises subjecting said gaseous hydrocarbon to a solid absorbent material, and cuprous chloride 1 at about a dull red heat, and simultaneously inducing a high frequency current in the'solid absorbent material, the high frequency inducedcurrent in conjunctionwith the catalyst at the elevated temperature causing the reaction to take place.

5. The process of converting gaseous hydro- .carborls into-liquid hydrocarbons which comprises subjectlng said gaseous hydrocarbon to a solid absorbent material, and ferrous chloride at about a dull red heat, and simultaneously inducing a high frequency current in the solid ob-V sorbent material, the; high frequency induced current in conjunction with the catalyst et-the elevated temperature causing the reaction toz take ulace'. I 6. The process of convertinggaseoushydrocarbons into liquid hydrocarbons which comprises subjecting said gaseous hydrocarbon to; a solid absorbent material, and nickel chloride at about a dull red heat, and slmultaneously'inducing a high frequency current in the solid absorbent material, the high frequency induced current in conjunction with the catalyst at the elevated temperature co. the reaction to take place. EUGENE C v 

